Composition of matter comprising resin esters



' 15 prepared an ment of the'toughened material in the pro- Patented May 1 1930 umrsofls' l-Arss TENT oFFr ca. i

may u. wanna," or NEWTON, massncnusnr'rs, nssronoa rro mre-ro's'rnaoouany, a OOBPORATIQN on NEW' armsny OOIPQSITION OI BATTER GOIIPRISING RESIN ESTEB S Q Io Drawing. Original application filed October 20, 1922, Serial No. 595,862. Divided and this filed June 14, 1929.

This invention relates to compositions comprising artificial resms and, cellulose esters, and relates especially to compositlons containi'ng artificial resins derived by reaction.

1 between organic acids and polyhydric al- "oohols.

This application is a division of my coending application Serial No. 595,862, filed ct. 20,1922, now Patent No. 1,722,776, of

10 July 30, 1929.

In; the present invention it'is an object to providea composition which has qualities of toughness, flexibility, extensibility and the like enablin tough spirit varnishes to be 5 also to permit of the employduc'tion of films, plastic compositions, molded articles and the like.

, .As is well known, nitrocellulose is incom- 20 patible with a great many substances. Most of the resins which dissolve in solvents for nitrocellulose are not miscible with the latter 7 and when a solution containing anysubstantial amount of resin and'nitrocellulose is allowed to dry the solid components segregate fand a worthless mass results. Of course, ni-' trocellulose. will assimilate small quantities of resins without eatl afiecting its toughness and flexibi ity, ut no substantial amounts may be added without impairing the qualities for which nitrocellulose is em- P oyed. T I have found that the rosin phthalic'glyceride resin will dissolve, mix or blend with nitrocellulose and apparently in almost any pro ortion. Hence itibecomes possible to intro uce nitrocellulose, pyroxylin, soluble cotton, celluloid .such'for example as scrap celas a toughening agent he addition of 10 to per cent ofsuch nitrocellulose compounds toa filmwhich is clear and may be luloid and used moving icture film to serve additional tou hness is desired. For examulose to the rosin phthalic glyceride. resin the. resin solution poured out ,on glass,

om the glass in its entirety. Still Serial Io. 371,054. v

be present in amounts of 40 30, 20, 10 per cent,

etc., as may be desired when films'of great toughness orspecial plastic products are required. The rosin phthalic glyceride resin I as ordinarily prepared is not as light-in color as good uantity nitrocelulose and-the tint resulting rom the presence of a lair e proportion of the rosin phthalic glyceri e resin is objectionable for some purposes, in which case the nitrocellulose may predominate.

There are many uses for such a material as for exam le varnishes, lacquers, japans,

application paints, su stitutes for hard rubber and va-- rious other molded plastic preducts, films for varlous purposes, as for exa le the windshields. of'automobiles and ot er purposes for'which films of this eneral character may be utilized app'rogriatedy.

The rosin pht alic glyceride resin in" a form readily soluble in a cohol,,acetone and the customary solvents of nitrocellulose, is of itself more readily afi'ected by water than nitrocellulose and" t e latter besides having a toughening and strengthening efiect, also cooperates with the rosin phthalic glyceride .resin to increase the resistance to water so that spotting or disintegration of the sur ace I through the action of water is not as likely to occur. On the other hand, the presence of a substantial or predominating amount of the rosin phthalic glyceride resin apparently reduces the inflammability and explosibility of; nitrocellulose to aconsiderable extent which, of course, purposes. 1 i In addition to rosinjIina of course, use other appropriate resins suc as '00 al resins wh ose-;esters are of a character a apted to admix with nitrocellulose or other cellulose esters or others. Thus I may prepare a. resin phthalic glyceride resin from con-goor other copal resin, phthalic acid and glycerine pre'ferably with the addition of some rosu'i to serve asa fluxin'g agent. While I have mentioned phthalic particularly,- it should be is advantageous for many roe tion is to render the rosin .10 polybasic aliphatic acids such as maleic, fuf

maric,-succinic, malic, citric, tartaric acids and the l1ke or aromatic acids of a d1bas1c character of which phthalic acidis an exam- 'ple. Benzoic acid and similar monobasic 15 acids maybe employedin some cases. A

The purpose of. hfemployment -of the mono or 'diba'sic acid in the esterification of the polyhydric "alcohol with a resin acid 'is probably clear from the'ifore ofing. Its funcphthalic glyceride resin soluble in nitrocellulose solventsand to make the resin phthalic glyceride resin capable of blending with-nitrocellulose whereby the latter may beemployed as a toughening :5 agent for the resin, (phthalic glyceride resin, or on the other ban the latter may be used as a means of modifying the character of nitrocellulose or cheapening it. The. addition of softening agents such as castor oil, earnphor, tri henyl or tricresyllphosphate, d1-

ethyl pht alate and the llkBlS not excluded although many useful compositions may be prepared without the addition of such so tening agents. Scrap celluloid conta ning camphor'or champhor substitute forms a cheap andreadily available toughening agent for the resinous com lex.

When" a solution of nitrocellulose in for example, acetone without a water eliminant such as fusel oil or amy acetate, is allowed'to dry a white, opaque film .usually forms. When a substantial proportion of the rosin phthalic glyceride resin of this invention .is present no such whitening and opacity is observed, a clear film being formed as though a special water elimmant had been added. I

To illustrate the toughening efiect' that the addition of small quantities of nitrocellulose 50. has on coatingsprepared from solutions of the'resin phthalic glyceride resin the following exam les are cited:

5 parts 0 soluble cotton mixed with 96 parts of the rosin phthalic glyceride resin coating was then'dried and allowed to harden for aperiod-ofj 24 hours. A similar coating was prepared from a, solution of the rosin phthalic glyceride resin, comparative tests made on the result coatin s. I'found mg a --.congo resin phthalic.-glyceride resin soluble in- Y that the addition enmspgaau amount of nitrocellulose toughenedthe resulting coating .cons'iderably. The. rosin glaithalic g1 .ceride Iresincoatingcouldreadily scratch witha were dissolved in acetone and the solution was allowed to fiow ona glass plate. 'The' sharp corneredflake ofsliellac while the coatin'g containing the nitrocellulose was not scratched. Coatings containing 10-per, cent, 20 per-cent, 33% er centaI 1 per cent nitrocellulose or so uble cottdn behavedin a similar manner.- All of the coatings were clear and transparent, the color varyin proportionally with the amount ofnitrooe lulose incorporated with the resin. The coatings containin 20 per cent and more of nitrocellulose coul be stripped. from the glass plates intact.

The rosin phthalic glyceride resin is miscible with nitrocellulose in all proportions, and

' as an illustration the following example is given:

'5 parts ofrosin phthalic glyceride resin and 95 parts of soluble cotton were dissolved in 2000 parts of acetone. A film prepared by flowing the solution on a glass late and allowing the film to dry .was slight more brittle than a film reparedfrom so uble cotton alone. The ad ition of one part of castor oil to the, solution, however remedied this defeet and the coating obtained was hard, tough, flexibleand trans arent. As an example of a varnish which is suitable for coating floors and the like the following is cited. 25 parts of rosin phthalic glyceride resin and. 50 parts of scrap motion picture film were dissolved in a solution consisting of a mixture of 100 parts of acetone and 50 parts of. benzol. The solution prepared in this manner was quite viscous but would flow readily at room temperature. A coating obtained by the use of thissolution was tough and transparent and light yellow in color.

As another example" a solution of parts of rosin phthalic glyceride resin, 10 parts of scrap motion picture film was dissolved in 14 parts of acetone. A coating obtained by the use of this solution was tou h, transparent and resistant to the action o water.

The condition of compatibility may be ascribed to a state of solid solution, that is, the nitrocellulose and the synthetic resin dissolvein one another. Such solid solution may form in the first instance when using a resin which is not compatible with nitrocellulose,

but on standing or through the action of light or other causes changes may occur due to separation or expulsion of one component from the immediate zone of the other and sub-- stantialideterioration thereupon result.

1. A composition of matter comprising a congo resin phthalic. glyceride resin soluble in nitrocellulose solvents, admixed with nitroiao nitrocellulose solvents, incorporated with ni-' glycerol ester of congo resin and phthalic acid incorporated with a cellulose ester.

4. A composition of matter comprising a glycerol ester of congo resin and phthalic' acid incorporated with a cellulose ester and a softening agent.

5. A composition of matter comprising a polyhydric alcohol ester. of congo resin and phthalic acid incorporated with a toughening agent containing nitrocellulose.

. 6. A composition of matter comprising :1

glycerol ester of a copal resin and an organic carboxylic acid, incorporated with nitrocellulose.

7. A composition of matter comprising 9. glycerol ester of a copal resin and an organic carboxylic acid, incorporated with a cellulose ester.

' 8. A composition of matter comprising a polyhydric alcohol ester of a copal resin and an organic carboxylic' acid, incorporated with nitrocellulose. g

9. A composition of matter comprising a glycerol ester of a copal resin and phthalic acid incorporated with nitrocellulose.

10. A composition of matter comprising a glycerol ester of rosin, congo resin and phthalic acid incorporated with a toughening agent comprising nitrocellulose.

o 11. A composition of matter comprising a glycerol ester of a copal resin and an organic diabasic acid with which is incorporated a toughening agent comprising nitrocellulose.

12. A varnish consisting of a'solution of a 5 glycerol ester of a copal resin and an organic carhoxylic acid incorporated with nitrocellulose.

13. A plastic s ubstancecomprising a glycerol ester of a copal resin and an organic 40 dibasic acid incorporated with nitrocellulose.

14. A plastic composition containing a copal phthalic glyceride resin which yields phthalic acid upon hydrolysis, admixed with nitrocellulose. I

15. A plastic composition containing a copaldibasic organic acidglyceride resin, which yields an organic diba'sic acid upon hydrol sis, admixed with nitrocellulose.

16. com osition of matter comprising the polyhydrlc alcohol ester of a copal resin and an organic carboxylic acid with which is incorporated a toughening agentcontaining a cellulose ester.

In testimony whereof, I have hereunto subscribed my name this 12th day of June, 1929.

HARRY WEBER. 

